Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

Mössbauer, X-ray diffraction and magnetization studies of Fe–Mn–Al–Nb alloys prepared by high energy ball milling

Fe₆₀Mn₁₀Al₂₀Nb₁₀, (Fe₆₀Mn₁₀Al₃₀)₉₅Nb₅ and (Fe₆₀Mn₁₀Al₃₀)₉₀Nb₁₀ ball milled powdered alloys were investigated using X-ray diffraction, Mössbauer spectrometry, thermomagnetic (TGM) and magnetization measurements. We studied the influence of Nb content and of different milling times on the structural and magnetic properties. Two main features can be concluded: (1) the FeAlMn induces a BCC phase whatever the Nb content is, and (2) as both increasing Nb content and milling time give rise to an highly disordered state in conjunction with a decrease of the ferromagnetic behavior.     

The extended loop group: An infinite dimensional manifold associated with the loop space

A set of coordinates in the non-parametric loop-space is introduced. We show that these coordinates transform under infinite dimensional linear representations of the diffeomorphism group. An extension of the group of loops in terms of these objects is proposed. The enlarged group behaves locally as an infinite dimensional Lie group. Ordinary loops form a subgroup of this group. The algebraic properties of this new mathematical structure are analyzed in detail. Applications of the formalism to field theory, quantum gravity and knot theory are considered.     

An analysis of reduced Hessian methods for constrained optimization

We study the convergence properties of reduced Hessian successive quadratic programming for equality constrained optimization. The method uses a backtracking line search, and updates an approximation to the reduced Hessian of the Lagrangian by means of the BFGS formula. Two merit functions are considered for the line search: the ₁ function and the Fletcher exact penalty function. We give conditions under which local and superlinear convergence is obtained, and also prove a global convergence result. The analysis allows the initial reduced Hessian approximation to be any positive definite matrix, and does not assume that the iterates converge, or that the matrices are bounded. The effects of a second order correction step, a watchdog procedure and of the choice of null space basis are considered. This work can be seen as an extension to reduced Hessian methods of the well known results of Powell (1976) for unconstrained optimization.This author was supported, in part, by National Science Foundation grant CCR-8702403, Air Force Office of Scientific Research grant AFOSR-85-0251, and Army Research Office contract DAAL03-88-K-0086.This author was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contracts W-31-109-Eng-38 and DE FG02-87ER25047, and by National Science Foundation Grant No. DCR-86-02071.     

The algebra of implicit operations

For an ordinal and a class of topological algebras of a given type (which may be infinite and may contain inflnitary operations), an-aryimplicit operation on is any new-ary operation whose introduction does not eliminate any continuous homomorphisms between members of . The set of all-ary implicit operations on is denoted by and forms an algebra of the given type which is endowed with the least topology making continuous all homomorphisms into members of . With this topology, is a topological algebra in which the subalgebra of all-ary operations on which are induced by terms is dense, provided that is closed under the formation of closed subalgebras and finitary direct products. This is obtained by realizing as an inverse limit of-generated members of . These results are applied to pseudovarieties of topological and finite algebras.This work was supported, in part, by INIC grant 85/CEX/4. This paper was written while the author was a faculty member at the Universidade do Minho.Presented by Ralph McKenzie.     

Palladium catalyzed Heck reaction of arenediazonium tetrafluoroborate salts with Baylis-Hillman adducts: production of α-benzyl-β-keto esters

A novel experimental procedure to obtain α-benzyl-β-keto esters from the Heck reaction between arenediazonium tetrafluoroborate salts and Baylis-Hillman (BH) adducts in the presence of Pd(OAc)₂ as catalyst is described. The methodology is simple, straightforward and the use of arenediazonium salts as opposed to conventional arylhalides/triflates over the usual Heck reaction is highlighted.     

Effect of the amine group on relative bond strengths in cubane and azacubanes

We have carried out an ab initio self-consistent-field molecular orbital study of the structures and relative bond strengths of some monoamine derivatives of cubane, azacubane, and 1,3-diazacubane. Our focus has been on the effect of the NH₂ group on the strengths of the endocyclic strained bonds in these molecules, and, in particular, on the conformation dependence of this effect. Our results show a consistent bond-weakening observed in one [and only one] C-C or C-N bond adjacent to the site of NH₂ substitution. We find that the particular bond that is weakened is in all cases essentially coplanar with the C-NH₂ bond and the position of the most negative electrostatic potential of the amine nitrogen. This direction-specific bond-weakening is viewed as an example of the anomeric effect.